Ternary Solvent System Research Articles

Comparative Study on the Solid Electrolyte Interface Formation by the Reduction of Alkyl Carbonates in Lithium Ion Battery

One of the major concerns in lithium ion battery is the composition of the electrolytes as it governs some of the vital physicochemical properties of the electrolytes such as viscosity, ionic conductivity, thermal stability and wettability. Most important properties of lithium ion batteries are related to the properties of the solid electrolyte interface (SEI) layer formed on the electrode surface. The SEI in turn is mainly dependent on the electrolyte composition [1]. Therefore, understanding the nature, mechanism and property of the SEI formation in different electrolyte composition is crucial in selecting electrolytes. In this work, we report a direct comparison of the reduction of propylene carbonate (PC), ethylene carbonate (EC) and diethyl carbonate (DEC) as a single, binary and ternary solvent systems. Battery performance test, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and scanning electron microscope (SEM) is employed to study the nature of the surface films formed. The reduction products are determined by using ex-situ attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), in the glove box, after employing linear sweep voltammetry (LSV) to certain potential regions. EC/PC/DEC based electrolyte shows better capacity retention and less impedance than the EC/PC system. In all systems, the FTIR results indicate the formation of (CH3CH2OCO2Li)2 and Li2CO3 due to the reduction of PC. EC is reduced to (CH2OCO2Li)2 and Li2CO3 in both the binary and ternary solvent system. The FTIR result at the potential where DEC reduction occurs shows the formation of (CH2=CH-OCO2CH2CH3)Li which is less stable and forms a less-passivating layer in the first cycle. However, this product can further react with another species in the subsequent cycles and form a stable SEI. [1] A.J. Gmitter, J. Gural, G.G. Amatucci, J. Power Sources, 217 (2012) 21-28.[2] K. Xu, J. Electrochem. Soc., 156 (2009) A751-A755.[3] G.V. Zhuang, H. Yang, B. Blizanac, P.N. Ross, Electrochem. Solid-State Lett, 8 (2005) A441-A445.

Parameter choice matters: validating probe parameters for use in mixed-solvent simulations.

Probe mapping is a common approach for identifying potential binding sites in structure-based drug design; however, it typically relies on energy minimizations of probes in the gas phase and a static protein structure. The mixed-solvent molecular dynamics (MixMD) approach was recently developed to account for full protein flexibility and solvation effects in hot-spot mapping. Our first study used only acetonitrile as a probe, and here, we have augmented the set of functional group probes through careful testing and parameter validation. A diverse range of probes are needed in order to map complex binding interactions. A small variation in probe parameters can adversely effect mixed-solvent behavior, which we highlight with isopropanol. We tested 11 solvents to identify six with appropriate behavior in TIP3P water to use as organic probes in the MixMD method. In addition to acetonitrile and isopropanol, we have identified acetone, N-methylacetamide, imidazole, and pyrimidine. These probe solvents will enable MixMD studies to recover hydrogen-bonding sites, hydrophobic pockets, protein–protein interactions, and aromatic hotspots. Also, we show that ternary-solvent systems can be incorporated within a single simulation. Importantly, these binary and ternary solvents do not require artificial repulsion terms like other methods. Within merely 5 ns, layered solvent boxes become evenly mixed for soluble probes. We used radial distribution functions to evaluate solvent behavior, determine adequate mixing, and confirm the absence of phase separation. We recommend that radial distribution functions should be used to assess adequate sampling in all mixed-solvent techniques rather than the current practice of examining the solvent ratios at the edges of the solvent box.

Ternary Deep Eutectic Solvents Tasked for Carbon Dioxide Capture

Task-specific ternary deep eutectic solvent (DES) systems comprising choline chloride, glycerol, and one of three different superbases were investigated for their ability to capture and release carbon dioxide on demand. The highest-performing systems were found to capture CO2 at a capacity of ∼10% by weight, equivalent to 2.3–2.4 mmol of CO2 captured per gram of DES sorbent. Of the superbases studied, 1,5-diazabicyclo[4.3.0]-non-5-ene (DBN) gave the best overall performance in terms of CO2 capture capacity, facility of release, and low sorbent cost. Interestingly, we found that only a fraction of the theoretical CO2 capture potential of the system was utilized, offering potential pathways forward for further design and optimization of superbase-derived DES systems for further improved reversible CO2 sequestration. Finally, the shear rate-dependent viscosities indicate non-Newtonian behavior which, when coupled to the competitive CO2 capture performance of these task-specific DESs despite a 1 to 2 orders o...

Comparative Study on the Solid Electrolyte Interface Formation by the Reduction of Alkyl Carbonates in Lithium ion Battery

Mixed alkyl carbonates are widely used as solvent for a various lithium-ion battery applications. Understanding the behavior of each solvent in the mixed system is crucial for controlling the electrolyte composition. In this paper, we report a systematic electrochemical and spectroscopic comparison of the reduction of propylene carbonate (PC), ethylene carbonate (EC), and diethyl carbonate (DEC) when used as single (PC), binary (EC/PC, EC/DEC), and ternary (EC/PC/DEC) solvent systems. The reduction products are identified based on Fourier transform infrared spectroscopy (FTIR) after employing linear sweep voltammetry to certain potential regions and their possible formation mechanisms are discussed. FTIR analyses revealed that the reduction of EC and PC was not considerably influenced by the presence of other alkyl carbonates. However, DEC exhibited a different reduction product when used in EC/DEC and EC/PC/DEC solvent systems. The reduction of EC occurred before that of PC and DEC and produced a passivating surface film that prevented carbon exfoliation caused by PC. Battery performance test, cyclic voltammetry, electrochemical impedance spectroscopy, and scanning electron microscope is employed to study the surface films formed. The binary EC/DEC solvent system demonstrated more favorable performance, smaller impedance, and higher Li+ ion diffusivity than did the other solvent systems used in this study.

Influence of Electrolyte Composition on Electrochemical Performance of Li-S Cells

The electrochemical performance of Li-S cells was investigated in various ternary electrolyte solutions composed of 1,2-dimethoxyethane (DME), tetra(ethylene glycol) dimethyl ether (TGM), and 1,3-dioxolane (DOX). The discharge capacity values and cycle data obtained at each composition were statistically treated with the Minitab program to obtain mixture contour plots, from which the optimal composition of the ternary solvent systems was predicted. The discharge capacities and capacity retention were quite dependent on the electrolyte composition. It was estimated from the contour plots of the capacity at 1.0 C that the discharge capacity sharply increased with a decrease in the TGM content. High capacities greater than 900 mAh/g at 1.0 C were expected for the electrolyte composition with a volume ratio of DME/TGM/DOX = 1/0/1. In contrast, it was predicted from the mixture contour plot of the capacity retention that the cycle performance would significantly increase with an increase in the DME content.

Ternary phase diagrams for aqueous mixtures of butyric acid with several solvents: Experimental and correlated data

Octan-1-ol, acetophenone, ethyl butanoate (ethyl butyrate), ethyl pentanoate (ethyl valerate), and 1,3-diethyl propanedioate (diethyl malonate) were used as solvents for determining the ternary liquid phase diagrams of aqueous mixtures consisting butyric acid, with the intention of bringing more effective and environmental friendly solvents into use. The liquid–liquid equilibrium (LLE) data for water+butyric acid+solvent ternary systems were investigated at 298.15K and atmospheric pressure. The ternary phase diagrams composed of solubility data and tie-lines were presented graphically. The reliability of the experimental tie-lines was tested by Othmer–Tobias correlation. The experimental tie-line data were compared with the results correlated by means of UNIQUAC model, and predicted by the UNIFAC method. It is concluded that the used solvents may be adequate extractants to extract butyric acid from its dilute aqueous solutions.

Simultaneous determination and screening of five pigments in marine phytoplanktons by high performance liquid chromatography-triple quadrupole mass spectrometry

A quantitative method based on high performance liquid chromatography coupled with electrospray ionization tandem triple-quadrupole mass spectrometry (HPLC-ESI-QqQ-MS) has been established for five pigments in marine phytoplanktons. The HPLC method used ternary solvent systems and a reversed-phase C16-amide column. In addition, methanol, acetonitrile and aqueous ammonium acetate were used as mobile phases. Five pigments (chlorophyll a, chlorophyll b, β, β-carotene, lutein and fucoxanthin) were quantified in selective reaction mode. As results, good linear relationships were achieved between the concentrations and the peak areas of the five pigment standards. And their correlation coefficients (r2) were higher than 0.996. The recoveries of the pigment standards were between 82.77% and 99.83%. The inter-day and intra-day precisions were lower than 5% (n = 5). The detection limits of the pigments for this method were between 0.02 and 0.16 μg/L and the quantification limits were in the range from 0.06 to 0.54 μg/L. According to the above method, eleven algae (Heterosigma akashiwo (NMBRah03-2), Heterosigma akashiwo (NMBRah03-2-2), Karlodinium veneficum (NMBjah047-1), Prorocentrum minimum ( NMBjah042), Nannochloropsis oceanic (NMBluh014), Chlorella pyrenoidosa (NMBluh015-1), Pleurochrysis sp. (NMBjih026-1), Prymnesium sp. (NMBjih029), Skeletonema costatum (NMBguh004-1), Thalassiosira weiss- flogii (NMBguh021) and Thalassiosira pseudonana) (NMBguh005)) have been investigated for comparing the pigment distributions. The method is sensitive, accurate, reproducible, and useful for the study of alga compositions.

Folding of bovine β-lactoglobulin in a ternary solvent system at subzero temperatures evaluated using the stopped-flow technique coupled with circular dichroism and intrinsic fluorescence

Folding of bovine β-lactoglobulin in a ternary solvent system at subzero temperatures evaluated using the stopped-flow technique coupled with circular dichroism and intrinsic fluorescence

Homogeneous Liquid–Liquid Microextraction for Determination of Organochlorine Pesticides in Water and Fruit Samples

A fast and effective preconcentration method for extraction of organochlorine pesticides (OCPs) was developed using a homogeneous liquid–liquid extraction based on phase separation phenomenon in a ternary solvent (water/methanol/chloroform) system. The phase separation phenomenon occurred by salt addition. After centrifugation, the extraction solvent was sedimented in the bottom of the conical test tube. The OCPs were transferred into the sedimented phase during the phase separation step. The extracted OCPs were determined using gas chromatography–electron capture detector. Several factors influencing the extraction efficiency were investigated and optimized. Optimal results were obtained at the following conditions: volume of the consolute solvent (methanol), 1.0 mL; volume of the extraction solvent (chloroform), 55 μL; volume of the sample, 5 mL; and concentration of NaCl, 5 % (w/v). Under optimal conditions, the preconcentration factors in the range of 486–1,090, the dynamic linear range of 0.01–100 μg L−1, and the limits of detection of 0.001–0.03 μg L−1 were obtained for the OCPs. Using internal standard, the relative standard deviations for 1 μg L−1 of the OCPs in the water samples were obtained in the range of 4.9–8.6 % (n = 5). Finally, the proposed method was successfully applied for extraction and determination of the OCPs in water and fruit samples.

A validated high-performance thin-layer chromatography method for the identification and simultaneous quantification of six markers from Platanus orientalis and their cytotoxic profiles against skin cancer cell lines

Betulinic acid (1), betulinic acid-3-acetate (2), 3-acetylbetulinaldehyde (3), oleanolic acid-3-acetate (4), 3-β-hydroxy-28,19-β-olenolide (5), and β-sitosterol (6) were isolated from Platanus orientalis and a high-performance thin-layer chromatography method was developed for their simultaneous quantification. The markers were first derivatized on the chromatogram with ceric ammonium sulfate and then high-performance thin-layer chromatography densitometry was carried out. Chromatographic separation of these markers was carried out on silica gel 60 plates using a ternary solvent system n-hexane/toluene/acetone (6:3.5:1 v/v/v) as a mobile phase. For marker 1, a deuterium (D2) lamp and wavelength of 420 nm was used. A tungsten (W) lamp was used for markers 2 and 3 at 550 nm and for 4-6 at 500 nm. The method was validated for accuracy, precision, LOD, and LOQ. All calibration curves showed a good linear relationship (r > 0.9919). The precision evaluated by an intra- and interday study showed RSDs < 2.51% and accuracy validation recovery between 95.54 and 99.33% with RSDs < 1.55%. The successful application of the validated method showed 1 as the most abundant component (4.63%) and 5 (0.017%) the least. The markers displayed a significant cytotoxic effect against human keratinocyte, mouse melanoma, and human skin epithelial carcinoma cancer cells by using a 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay.

Spectrophotometric Determination of Trace Zn(II) with Phenanthraquinone Monophenyl Thiosemicarbazone Following Homogeneous Liquid-Liquid Extraction in the Water-Acetic Acid-Chloroform Ternary Solvent System

Spectrophotometric Determination of Trace Zn(II) with Phenanthraquinone Monophenyl Thiosemicarbazone Following Homogeneous Liquid-Liquid Extraction in the Water-Acetic Acid-Chloroform Ternary Solvent System

Direct imaging of plant metabolites in leaves and petals by desorption electrospray ionization mass spectrometry

Two different approaches to direct imaging of plant material with desorption electrospray ionization (DESI) mass spectrometry are presented and demonstrated on leaves and petals of Hypericum perforatum. The direct imaging approaches are in contrast to previous DESI imaging studies where indirect analysis via imprints were used in order to overcome the morphological barrier presented by the layer of cuticular waxes covering the surface of a leaf or a petal. In order to enable direct imaging of such plant materials, a new ternary solvent system is introduced, providing a higher and more stable signal from soft plant materials than the binary solvent systems typically used in DESI. With this ternary solvent system, it was possible to image a number of very long chain fatty acids (VLCFAs), a significant class of metabolites located in the cuticle layer in leaves and petals, as well as other plant metabolites. In the case of the petals of H. perforatum, all common metabolites could be imaged directly using the ternary solvent, whereas in the case of leaves from the same plant, only some of the metabolites were accessible, even with the ternary solvent system. For these samples, the leaves could be imaged with direct DESI after chloroform had been used to remove most of the cuticle, thus exposing lower layers in the leaf structure. A number of considerations regarding selection of samples and instrumental parameters that must be made in direct DESI imaging of plant materials are discussed.

Preparation of protein loaded chitosan microparticles by combined precipitation and spherical agglomeration

Abstract Combined precipitation and spherical agglomeration was carried out in the non-miscible region of ethyl acetate–ethanol–water ternary solvent system. At first, w/o type quasi emulsion was prepared by sequential introduction of aqueous solutions of human serum albumin (HSA), chitosan (CS), and poly(4-styrenesulfonate) (PSS) into an ethyl acetate–ethanol solvent mixture. HSA was used to model a protein type drug, while CS and PSS served as matrix material in the obtained composite particles. PSS also served as chemical precipitation agent for both of the HSA and CS. The solubility of all these substances was reduced by introduction of additional amounts of ethyl acetate–ethanol mixture and/or ethanol as poor solvents. Due to the counter-diffusion of the good and poor solvents between the water rich droplets and the ethyl acetate–ethanol rich continuous phase, the aqueous phase gradually disappeared and partial agglomeration of the precipitated solids and their transfer to the continuous organic phase took place. The paper gives a report on the effect of several process variables on the quality of the obtained microparticles, such as their shape and stability against disintegration. The effects of the composition of the ternary solvent mixture, the route of its variation, the feeding method and composition of the added poor solvents, the stirring rate and the duration of agitation were studied.

Chemical recycling of polycarbonate wastes into bisphenol A by using green solvent composition

Polycarbonate contained in waste compact discs (CDs) and digital versatile (video) discs (DVDs) have been chemically recycled into bisphenol A (BPA) — using a ternary solvent system: glycerin, sorbitol, water under conventional heating method. The obtained results show that the mixture of glycerin, sorbitol, water in the ratio 6:3:1 undergoes recycling with high yield within 45 minutes. The recovered BPA was identified by spectroscopic methods and the results were compared with the data corresponding to standard sample.

Kinetics-controlled growth of aligned mesocrystalline SnO2 nanorod arrays for lithium-ion batteries with superior rate performance

A general method for facile kinetics-controlled growth of aligned arrays of mesocrystalline SnO2 nanorods on arbitrary substrates has been developed by adjusting supersaturation in a unique ternary solvent system comprising acetic acid, ethanol, and water. The hydrolysis processes of Sn(IV) as well as the nucleation and growth of SnO2 crystals were carefully controlled in the mixed solvents, leading to an exclusively heterogeneous nucleation on a substrate and the subsequent growth into mesocrystalline nanorod arrays. In particular, aligned arrays of hierarchically structured, [001]-oriented mesocrystalline SnO2 nanorods with four {110} lateral facets can be readily grown on Ti foil, as well as many other inert substrates such as fluoride-doped tin oxide (FTO), Si, graphite, and polytetrafluoroethylene (Teflon). Due to the unique combination of the mesocrystalline structure and the one-dimensional nanoarray structure, the obtained mesocrystalline SnO2 nanorod arrays grown on metallic Ti substrate exhibited an excellent rate performance with a high initial Coulombic efficiency of 65.6% and a reversible capacity of 720 mA·h/g at a charge/discharge rate of 10 C (namely, 7,820 mA/g) when used as an anode material for lithium-ion batteries.

Synthesis and Characterization of Monetite Prepared Using a Sonochemical Method in a Mixed Solvent System of Water/Ethylene Glycol/N,N-Dimethylformamide

Bioactive monetite (anhydrous calcium hydrogen phosphate, CaHPO4) has been successfully synthesized using the sonochemical method in the presence of a ternary solvent system of water/ethylene glycol (EG)/N,N-dimethylformamide (DMF). The morphology and chemical composition of the synthesized powders were characterized using field emission scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. The results indicated that with increasing sonication time, the morphology changed slightly from a plate-like one to a combination of plates (flower-like). The formation of flower-like nanosheets requires an optimum time of 40 minutes, and the nanosheets have an average thickness of 210 ± 87 nm. The concentration of DMF clearly influences the morphology and crystal phase of the products. The ideal product was obtained using a water/EG DMF ratio of 1:2.

Vapour-Liquid Equilibrium for Novel Solvents for CO2 Post Combustion Capture

Vapor-liquid equilibrium (VLE) for two binary aqueous solutions of novel CO2 capture solvents were studied experimentally in a modified Swietoslawski ebulliometer at 70, 80 and 100°C for one compound (Compound A) and at 50, 60, 80 and 100°C for another compound (Compound B). The total pressure (P) as function of temperature (T) was measured for these binary solutions and the composition of the vapor (y) and liquid (x) phases were analyzed. Experimental P-T data were fitted to an Antoine equation.Experimental activity coefficients for Compound A were calculated using P, T, x, y data and activity coefficients for Compound B were calculated using only P, T, x data. Activity coefficients of Compound A and D were fitted to Wilson and NRTL models.The total pressure (P) as a function of temperature (T) was measured for one novel ternary solvent system, containing Compound A, B and water at a certain concentration ratio.

Utilization of homogeneous liquid–liquid extraction followed by HPLC-UV as a sensitive method for the extraction and determination of phthalate esters in environmental water samples

A simple and sensitive method for the extraction of four phthalate esters including dimethyl phthalate (DMP), diethyl phthalate (DEP), benzyl butyl phthalate (BBP) and di-n-butyl phthalate (DBP) as well as their determination in water samples was developed using homogeneous liquid–liquid extraction (HLLE) and HPLC-UV. The extraction method is based on the phase separation phenomenon by the salt addition to the ternary solvent system. The extraction parameters such as type and volume of extracting and consolute solvent, concentration of salt, pH of sample and extraction time were optimized. Under the optimal conditions (extraction solvent: 100 µL CHCl3; consolute solvent: 2.0 mL methanol; NaCl 15% (w/v) and pH of sample: 6.5) extraction recovery was in the range of 92–102%. Linearity was observed in the range of 0.5–300 µg L−1 for DEP and 0.6–300 µg L−1 for DMP, BBP and DBP. Correlation coefficients (r 2), limits of detection (LODs) and relative standard deviations (RSDs) were in the ranges of 0.9976–0.9993, 0.18–0.25 and 1.5–4.8%, respectively. The method was successfully applied for the preconcentration and determination of these phthalate esters in the several environmental water samples.

Dispersive liquid-liquid microextraction for simultaneous determination of cadmium, cobalt, lead and nickel in water samples by inductively coupled plasma optical emission spectrometry

We report on a new method for the dispersive liquid-liquid microextraction of Cd(II), Co(II), Pb(II) and Ni (II) from water samples prior to their simultaneous determination by inductively coupled plasma optical emission spectrometry (ICP-OES). The procedure is based on the injection of a ternary solvent system composed of appropriate quantities of extraction solvent (trichloroethylene), dispersive solvent (ethanol), and the chelating reagent 2-(2′-benzothiazolylazo)-p-cresol into the sample solution. The solution turns turbid immediately after injection, and the analytes are extracted into the droplets of the organic phase which was dried and dissolved in a mixture of Triton X-114, nitric acid, and ethanol. The metal ions in this mixture were quantified by ICP-OES. The detection limits under optimized conditions are 0.2, 0.3, 0.2 and 0.7 μg L−1 for Cd(II), Co(II), Pb(II) and Ni(II), respectively. The enrichment factors were also calculated for Cd (13), Co (11), Pb (11) and Ni (8). The procedure was applied to the determination of cadmium, cobalt, lead and nickel in certified reference material (waterway sediment) and water samples.

Ionic liquid-based ultrasound-assisted dispersive liquid–liquid microextraction followed high-performance liquid chromatography for the determination of ultraviolet filters in environmental water samples

In the present study, a rapid, highly efficient and environmentally friendly sample preparation method named ionic liquid-based ultrasound-assisted dispersive liquid–liquid microextraction (IL-USA-DLLME), followed by high performance liquid chromatography (HPLC) has been developed for the extraction and preconcentration of four benzophenone-type ultraviolet (UV) filters (viz. benzophenone (BP), 2-hydroxy-4-methoxybenzophenone (BP-3), ethylhexyl salicylate (EHS) and homosalate (HMS)) from three different water matrices. The procedure was based on a ternary solvent system containing tiny droplets of ionic liquid (IL) in the sample solution formed by dissolving an appropriate amount of the IL extraction solvent 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIM][FAP]) in a small amount of water-miscible dispersive solvent (methanol). An ultrasound-assisted process was applied to accelerate the formation of the fine cloudy solution, which markedly increased the extraction efficiency and reduced the equilibrium time. Various parameters that affected the extraction efficiency (such as type and volume of extraction and dispersive solvents, ionic strength, pH and extraction time) were evaluated. Under optimal conditions, the proposed method provided good enrichment factors in the range of 354–464, and good repeatability of the extractions (RSDs below 6.3%, n=5). The limits of detection were in the range of 0.2–5.0ngmL−1, depending on the analytes. The linearities were between 1 and 500ngmL−1 for BP, 5 and 500ngmL−1 for BP-3 and HMS and 10 and 500ngmL−1 for EHS. Finally, the proposed method was successfully applied to the determination of UV filters in river, swimming pool and tap water samples and acceptable relative recoveries over the range of 71.0–118.0% were obtained.